EP3383529A1 - Conversion photocatalytique de dioxyde de carbone et d'eau en hydrocarbure(s) substitué(s) ou non substitué(s) - Google Patents

Conversion photocatalytique de dioxyde de carbone et d'eau en hydrocarbure(s) substitué(s) ou non substitué(s)

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Publication number
EP3383529A1
EP3383529A1 EP16869409.9A EP16869409A EP3383529A1 EP 3383529 A1 EP3383529 A1 EP 3383529A1 EP 16869409 A EP16869409 A EP 16869409A EP 3383529 A1 EP3383529 A1 EP 3383529A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogen
pph
production
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16869409.9A
Other languages
German (de)
English (en)
Other versions
EP3383529A4 (fr
Inventor
Gregory F. METHA
Gunther ANDERSSON
Vladimir Golovko
Thomas Nann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Flinders University of South Australia
University of South Australia
Adelaide Research and Innovation Pty Ltd
University of Canterbury
Original Assignee
Flinders University of South Australia
University of South Australia
Adelaide Research and Innovation Pty Ltd
University of Canterbury
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2015904952A external-priority patent/AU2015904952A0/en
Application filed by Flinders University of South Australia, University of South Australia, Adelaide Research and Innovation Pty Ltd, University of Canterbury filed Critical Flinders University of South Australia
Publication of EP3383529A1 publication Critical patent/EP3383529A1/fr
Publication of EP3383529A4 publication Critical patent/EP3383529A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • B01J37/16—Reducing
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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    • B01J2531/0213—Complexes without C-metal linkages
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    • B01J37/02—Impregnation, coating or precipitation
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
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    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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Definitions

  • the present invention relates to the production of hydrocarbon(s) such as methane or substituted hydrocarbon(s) such as methanol.
  • the hydrocarbon(s) can be formed using water and carbon dioxide as precursor materials.
  • Carbon dioxide has received much attention as an alternative feed stock for the production of methane, because there is a drive to reduce carbon dioxide emissions to help slow global warming, and because it is cheap and readily available. Carbon dioxide can be converted into hydrocarbons such as methane by reacting it with hydrogen, for example via the Sabatier reaction.
  • hydrocarbons produced can then be converted into other forms such as methanol.
  • a method for the production of hydrocarbon(s), such as methane, or substituted hyd rocarbons, such as methanol comprising the steps of: contacting a catalyst with water and carbon dioxide in the presence of light in order to photocata lyse :
  • a method for the production of hyd roca rbon(s), such as metha ne, or substituted hydrocarbons, such as methanol comprising the steps of: a. contacting a first catalyst with water in order to photocatalyse the splitting of at least some of the water into hydrogen and oxygen;
  • step (a) at least some of the hydrogen ca n be produced from step (a), in order to photocatalyse the reaction between the hydrogen and carbon dioxide to produce hydroca rbon(s), such as methane, a nd/or substituted hydrocarbons, such as methanol.
  • hydroca rbon(s) such as methane, a nd/or substituted hydrocarbons, such as methanol.
  • the first and second catalyst can be the sa me catalyst.
  • the first catalyst a nd the second catalyst ca n be different cata lysts.
  • the first a nd second cata lysts can comprise one or more nanoclusters.
  • the first and second catalysts can be immobilized on the support.
  • the first a nd second catalysts can be activated on the support.
  • the nanoclusters can comprise gold and/or ruthenium nanoclusters.
  • the nanoclusters can have an average cluster size of less than about 2 nm .
  • splitting of at least some of the water into hydrogen and oxygen can include splitting the water into hydrogen and or oxygen containing species such as hydrogen radicals, hydronium a nd or hydroxyl radicals.
  • a method for the production of hydrocarbon(s), such as methane, or substituted hydrocarbons, such as methanol comprising the steps of: a, contacting a first photocatalyst with water in the presence of light in order to
  • the photocatalyse the splitting of at least some of the water into hydrogen and oxygen; wherein the first photocatatyst comprises gold nanoclusters supported by a titanium dioxide substrate;
  • step (b) contacting a second catalyst with a gas stream comprising carbon dioxide and at least some of the hydrogen produced from step (a) in order to catalyse the reaction between the hydrogen and carbon dioxide to produce hydrocarbon(s), such as methane, and/or substituted hydrocarbons, such as methanol;
  • the second catalyst comprises ruthenium nanoclusters supported by a titanium dioxide substrate.
  • the catalyst can comprise a first catalyst and a second catalyst.
  • the first catalyst can be a photocatalyst.
  • the second catalyst can be a photocatalyst.
  • the first photocatalyst preferred for use in step (a) above can comprise a substrate and an active metal component.
  • the substrate can be graphene, graphite, carbon black, nanotubes, fullerenes, and/or zeolites.
  • the substrate can be a carbon nitrate CxNy.
  • the substrate can be a metal oxide or nitride.
  • the substrate can be a titania, silica and/or alumina.
  • the substrate can be barium titanate or perovskite.
  • the substrate can be a titanium oxide.
  • the titanium oxide support substrate can include anatase and/or the commercialiy available P25.
  • the substrate can be a monolithic.
  • the substrate can have a planar surface such as a plate or disc.
  • the substrate can be particulate.
  • the substrate can comprise nanoparticles. In one embodiment, the substrate comprises titanium dioxide nanoparticles.
  • Photocatalysts are activated by light.
  • the light used can be determined by the specific type of photocatalysts.
  • the first photocatalyst comprises two or more types of photocatalyst where one can perform at a specific wavelength and the other can perform over a broad wavelength range
  • the more intense the light the more efficient the catalytic process is.
  • the reactants and/or products may be degraded if the light source is too intense. Therefore, it can be advantageous to have a balance between rate of catalysis and the rate of degradation of the reactants/products.
  • a common wavelength range for photocatalysts are those in the ultraviolet range i.e. 200-400 nm.
  • the source of ultraviolet light may be from a dedicated lamp or may be from a natural light source, such as the sun.
  • Usually commercial ultraviolet light sources have a greater intensity compared to natural sources.
  • Natural light sources can have a UV intensity (i.e. ⁇ 400 nm) of approximately 4.63 mW cm "2 , while commercial sources can be many times more intense, such as >1000 mW cm "2 .
  • Using a natural light source can be advantageous from an energy input perspective, and can make the process more environmentally friendly. If a natural light source is used, it may be supplemented with a commercial light source. Such circumstances may include during times of inclement weather and/or during times of reduced light activity, such as at night. In areas with plentiful natural light, e.g.
  • Concentrated solar sources can provide energies in the range of from about 500 to about 1000 suns i.e. 2315 -4630 mW/cm "2 .
  • An advantage of using photocatalysts is that they often do not require the use of heat to catalyse reactions. Not requiring heat can decrease operational costs, make the production of hydrogen more environmentally friendly, and make the production of hydrogen safer. Temperatures that can be used for photocatalysis are around room temperature e.g. about 20-30 "C, but may be as high at about 100-300 °C, for example 250 °C. Nevertheless, the photocatalyst could be used with the addition of heat, which may allow for a reduction in light energy input.
  • the active metal of the photocatalyst can be selected from gold, silver, copper, platinum, palladium, nickel, rhenium, ruthenium and/or titanium, and/or other transition metals and their corresponding oxides.
  • the active metal is gold. It may be advantageous to have more than type of active metal, one of which could be gold. Whilst gold is exemplified herein, it should be understood that the invention is not so limited and other active metal nanoclusters could be prepared using the details disclosed herein.
  • the form in which the active metal is associated with the substrate can be determined by the reaction
  • the active metal(s) could be present in the form of complexes, nanoparticles and/or clusters/nanoclusters. It may be advantageous to have more than one active metal where each metal has a different form. In a preferred embodiment, the active metal is present as a nanocluster.
  • metal complexes have an active metal that is surrounded by one or more ligand(s).
  • the type of ligand(s) can greatly affect the performance of the catalyst.
  • One of the ligands can be immobilised on the surface of the substrate, which can help to prevent the complex from disassociating from the substrate. This can be advantageous, for example, in helping to recover the photocatalyst once a reaction is complete.
  • Nanoparticles on the other hand, can have an average size in a range of from about 5 to about 100 nm. The shape and arrangement of the nanoparticles can greatly affect the function as a photocatalyst.
  • a nanoparticle with a cuboid shape usually has a lower surface area compared to nanoparticles that are rods or ribbons, and a lower surface area is usually associated with a decrease in catalyst efficiency.
  • Clusters or nanoclusters refer to a collection or group of two or more active metal atoms, but usually contain less than approximately 200 atoms. Clusters typically differ from nanoparticles both structurally and electronically - unique packing of atoms not seen in larger metal particles and non-piasmonic (Au/Ag)/metallic. It terms of size, nanoclusters are usually considered as being between complexes and nanoparticles.
  • the number of atoms used to describe a nanocluster is the average number and there is typically a distribution associated with the average number.
  • nanoclusters containing more than 20 metal atoms can have a distribution of ⁇ 10 or more percent e.g. M30 ⁇ 3, 55 ⁇ 5, 100 ⁇ 10.
  • the metals that comprise the nanoclusters can comprise ligands. Similar to complexes, any ligands associated with the nanocluster can be used to stabilise the nanocluster and in some circumstances may help to improve the performance of the nanocluster when as a catalyst. In some cases, it is preferred to remove any ligands before the compound is used as a photocatalyst.
  • the first photocatalyst can have a support that is photoactive.
  • the clusters can be deposited onto a support capable of adsorbing light of appropriate wavelength.
  • the cluster plus the photoactive support forms the photocatalyst.
  • the support can be particulate itself or is can be a bulk solid substrate.
  • the bulk solid substrate can be a wafer such as a silicon wafer or a porous silica disk.
  • the first photocatalyst in the form of a paste can be applied to the support. The thickness of the applied photocatalyst can be varied.
  • the photocatalyst comprises a titanium dioxide substrate in the form of nanoparticles; the nanoparticles are associated with gold nanoclusters.
  • the gold nanoclusters can comprise Au 3 to Auioi.
  • the gold clusters can be selected from (Ph 3 Pau) 3 OBF4, [(AuPPh 3 ) 3 0]PF 6 ,
  • Au 5 (PPh 3 )4CI Au 6 (PPh 3 (BF ⁇ ) 2 , Au s ⁇ PPh 3 lv1NOs)2, Au 6 ⁇ PPh 3 ) 6 (PF 6 )2, Au 8 (PPh 3 ) 8 (N0 3 )_, ⁇ 8 ( ⁇ 3 ) 7 ( ⁇ 0 3 ) 2 , Au 9 (PPh 3 ) s (N0 3 ) 3 , Auio(PPh 3 ) 5 (C 6 Fs)4, AuuClsifm-CFaCeH ⁇ ) ⁇ ?, Aun(PPh 3 ) 7 (PF 6 ) 3 ,
  • the activity of the photocatalyst may decrease.
  • the nanoclusters have an average size of less than about 2.5, 2, 1.5 or 1 nm.
  • the average size of e.g. Auioican be approximately 1,6 nm.
  • the number of nanoclusters per substrate nanoparticle may depend on the type of active metal used. In one embodiment, the number of nanoclusters per nanoparticle is at least about 1, 2, 5, 10, 15, 20, 15 or 30.
  • the percentage approximate coverage of the nanoparticles with nanoclusters can be in the range of from about 0.1 to about 10 % or more, or at least about 0.1, 0.5, 1, 17, 2, 3, 4, 5, 6 or 10 % or more as a percentage of the total available surface area. In one embodiment, the approximate coverage of the nanoparticles with gold nanoclusters is in the range of from about 0.17 to about 1.7 wt%.
  • the first photocatalyst can be pre-treated prior to use.
  • Treatment methods can include calcining and/or acid treatment. Acid treatment can be performed with or without calcining. Where calcining is used, acid treatment can be performed before or after calcining. It is thought that acid treatment has an effect on the interaction between the catalyst substrate and the active metal during preparation of the photocatalyst.
  • Calcining can be performed at a temperature of at least about 50, 100, 200, 300 or 400 °C to remove any residual carbon contamination from the photocatalyst surface. Calcining can be performed under oxygen and/or hydrogen atmospheres and/or under vacuum. There is thought to be an improvement in i gas production as the first photocatalyst is treated under successively harsher conditions. This may be due to the removal of any ligands from the photocatalyst surface (leaving only the active metal clusters behind). It is hypothesised that in some embodiments, the removal of ligands and an increase in cluster size improves the catalytic performance of anatase-supported Au clusters.
  • the first photocatalyst can be advantageous to expose to a vacuum for an extended prior of time.
  • the first photocatalyst Prior to use the first photocatalyst can be held under vacuum for at least about 1, 2, 5, 10, 12 or 15 hours. It is preferred that the photocatalyst is not exposed to the atmosphere once it has been held under vacuum.
  • the step of contacting the first photocatalyst with water can involve exposing all or some of the surfaceisl of nhotocatalyst with water in order to effect a reaction.
  • the water can be from any source.
  • the water can be substantially pure, or it can be a part of an aqueous solution.
  • the water used to produce hydrogen can be in liquid form and/or vapour form.
  • the step of contacting the photocatalyst with water comprises immersing the photocatalyst in a body of water.
  • the water can flow over the first photocatalyst.
  • the flow can be continuous.
  • the first photocatalyst may be homogenously or heterogeneously distributed in the body of water.
  • Homogenous distribution may be performed by vigorously mixing the body of water and a first photocatalyst in a fine particulate form.
  • the first photocatalyst can be an aggregate that can easily be separated from the body of water.
  • Heterogeneous distribution may be achieved by immobilising the first photocatalyst on at least one stationary support.
  • the first photocatalyst is supported on rods that can be inserted into the body of water.
  • the step of contacting the first photocatalyst with water includes allowing a water vapour to come into contact with the first photocatalyst.
  • Bringing the water vapour into contact with the first photocatalyst can be performed in a variety of ways, for example, continuously flowing water vapour over the first photocatalyst.
  • the pressure of the water vapour can be varied to achieve the desired result (optimum hydrogen production). Condensation of water vapour can occur if the pressure of the vapour is too high. To prevent condensation, the heat of the vapour may be increased, but applying too much heat to prevent condensation may be undesirable.
  • the water vapour may be provided at below atmospheric pressures.
  • step (a) is performed under 20 Torr of water vapour. Additional gases may be included with the water vapour.
  • the additional gas may be an inert gas.
  • the inert gas can be argon (Ar). !n one embodiment, step (a) s performed under 280 Torr of argon (Ar).
  • oxygen is also produced according to the following equation (1):
  • the hydrogen and oxygen gases can be collected and stored for use in a subsequent reaction.
  • the subsequent reaction can be the reaction of at least some of the hydrogen with carbon dioxide in an e.g. 4:1 molar ratio of hydrogen to carbon dioxide to produce hydrocarbons such as methane.
  • all of the hydrogen is passed to a further reaction to assist in the production of methane.
  • the amount of hydrogen that can be produced in step (a) can be at least about 15, 50, 80, 100, 150, 200, 250, 350, 450, 550, 1000, 1500, 2000 or 5000 ⁇ hr 1 g ⁇ cm -2 .
  • the hydrogen produced in step (a) can be used as feed for the production of unsubstituted hydrocarbons.
  • Hydrocarbons can include Ci to Cio containing compounds such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, their various isomeric forms such as n-, iso-, sec- and tert-alkanes, and their respective oxides such as methanol and ethanol. More complex hydrocarbons such as aromatics may also be produced.
  • the hydrocarbons produced can be greater than Cio.
  • the hydrogen can also be used as a feed for the formation of a substituted hydrocarbon such as methanol, ethanol, propanol, and so on.
  • the step of contacting the second catalyst with carbon dioxide and hydrogen can involve allowing the gas streams to flow over the surface.
  • the amount of gas introduced to the surface of the second photocatalyst can be controlled (in terms of molar ratio) so as to ensure the desired reaction product. Steps (a) and (b) can be undertaken sequentially as two separate method steps, or they can be undertaken concurrently.
  • the second catalyst can be a photocatalyst.
  • the photocatalyst can be activated by UV wavelengths of light.
  • the second catalyst preferred for use in step (b) can comprise a substrate and an active metal component.
  • the substrate can be as described above e.g. graphene, graphite, carbon black, nanotubes, fuilerenes, and/or zeolites.
  • the substrate can be an oxide or a nitride.
  • the substrate can be titania, silica and/or alumina and their oxides.
  • the substrate can be a titanium oxide.
  • the titanium oxide support can include anatase and/or the commercially available P25.
  • the substrate can be a planar surface or it could be particulate.
  • the substrate can comprise nanoparticles. In one embodiment, the substrate comprises titanium dioxide nanoparticles.
  • the active metal of the photocatalyst of step (b) can be selected from gold, copper, silver, platinum, palladium, nickel, rhenium, ruthenium and/or titanium, and/or other transition metals and their corresponding oxides and/or other transition metals and their corresponding oxides.
  • the active metal is ruthenium. It may be advantageous to have more than type of active metal, where at least ruthenium is present.
  • the second catalyst can be applied to a support.
  • the support can be a particulate to increase the surface area, or the support can be solid substrate.
  • the solid substrate can be a wafer such as a silicon wafer or a porous silica disk.
  • the second catalyst can be applied to the support as a layer. The thickness of the layer can be varied.
  • the form in which the active metal is supported on the substrate can be determined by the reaction and/or the reaction conditions.
  • the active metal(s) may be present in forms of complexes, nanoparticles and/or nanoclusters. These forms of active metal are described in relation to step (a) above and that description also applies here. It may be advantageous to have more than one active metal, with each metal having a different form i.e. nano clusters and complexes.
  • the active metal is present as a ruthenium nanocluster.
  • the second catalyst comprises a titanium dioxide substrate in the form of nanoparticles associated with ruthenium nanoclusters.
  • the percentage of ruthenium nanoclusters loaded onto the nanoparticles can be at least about 0.1, 0.2, 0.5, 1, 2, 5 or 10 wt%.
  • the second catalyst can be pre-treated prior use.
  • Treatment methods can include calcining and/or acid treatment. To help ensure contaminates are removed from the catalyst prior to use, it can be advantageous to expose the catalyst to a vacuum for an extended prior of time. Calcining can be performed for a period of at least about 1, 2, 5, 10, 12 or 15 hours.
  • the pre-treatment can be at a temperature of at least about 50, 100, 200, 300 or 400 °C to remove any residual carbon
  • Calcining can be performed under oxygen and/or hydrogen atmospheres and/or under vacuum. This may be due to the removal of any ligands from the photocatalyst surface (leaving only the active metal clusters behind). It is hypothesised that in some embodiments, the removal of ligands and an increase in particle size improves the catalytic performance of anatase-supported u clusters.
  • a ruthenium-based catalyst may significantly reduce the temperatures and/or pressures required to produce methane and/or methanol. For example, temperatures less than about 100, 200 or 250 °C with pressure below a few atmospheres can be used with ruthenium-based catalysts to produce hydrocarbons (substituted or unsubstituted) from hydrogen.
  • the efficiency of a ruthenium-based photocatalyst may also be improved by exposure to ultraviolet light.
  • the support may assist in the photocatalytic production of hydrocarbon or substituted hydrocarbons.
  • the amount of methane that can be produced in step (b) can be at least about 350, 450, 550, 1000, 2000 or 5000 ⁇ hr 1 g ⁇ crrf 2 .
  • the reaction of steps (a) and (b) may be performed in an apparatus (a reactor).
  • the apparatus for step (a) can have an inlet for the introduction of water.
  • the first photocatalyst of step (a) may be housed in a part of the apparatus and arranged so that the water can come into contact with the surface of the first photocatalyst.
  • the apparatus is seaiable once the water has been introduced.
  • the water can be introduced as a liquid or vapour. If the water is a vapour it can be introduced under pressure.
  • a light source can be arranged inside or outside of the vessel to allow activation of the first photocatalyst.
  • the reaction may be allowed to proceed for as long as is necessary to produce as much hydrogen as is required (or as is stoichiometricaliy possible).
  • the temperature and/or pressure within the reactor may be slowly increased to effect the optimal reaction.
  • the gases evolved in the reactor may be collected from the apparatus from an outlet. The gases may be collected and separated.
  • a second apparatus may be provided for step (b).
  • step (b) carbon dioxide and hydrogen are mixed at the desired molar ratio in the presence of a second photocatalyst.
  • the second photocatalyst may be housed in a part of the apparatus and arranged so that the gas streams can come into contact with the surface of the photocatalyst.
  • the apparatus is seaiable once the gases have been introduced.
  • a light source can be arranged inside or outside of the vessel to allow activation of the second photocatalyst.
  • the reaction may be allowed to proceed for as long as is necessary to produce as much product as is required.
  • the temperature and/or pressure may be slowly increased in the apparatus to effect reaction.
  • the gases evolved may be collected from the apparatus from an outlet. The gases may be collected and separated.
  • step (a) and step (b) the apparatus can be an autoclave. in one embodiment step (a) and step (b) are performed in the same apparatus. Because the production of hydrogen is photocatalytic, it may be possible to employ both the first photocatalyst and the second photocata!ysts to produce both hydrogen and hydrocarbons at the same time, sequentially.
  • the two photocatalysts, first and second may be independent of each other, or they may be associated. If the two catalysts are associated with each other, it may be that, for example, gold clusters and ruthenium nanoclusters are supported on the same titanium dioxide support. In some embodiments, there are gold ruthenium nanoclusters as described further below. Having one support with two active nanoclusters or one support with active Au-Ru nanoclusters may reduce the operational costs of the production of hydrocarbons and may make the process more
  • step (a) the molar ratio of hydrogen to carbon dioxide is always greater for any carbon dioxide produced during the production of hydrogen.
  • any carbon dioxide produced during the production of hydrogen is preferably supplemented with an additional source of carbon dioxide. If the production of hydrocarbons is coupled with a production that burns hydrocarbons e.g. for electricity, then the products from one process may be a feed stock for another.
  • steps (a) and (b) occur at the same catalyst site.
  • the method of the present invention can be undertaken in the presence of a catalyst which can
  • hydrocarbon(s) such as methane, and/or substituted hydrocarbons, such as methanol
  • the catalyst can comprise a substrate and an active metal component.
  • the substrate can be as described above with respect to the other catalysts.
  • the substrate can be e.g. graphene, graphite, carbon black, nanotubes, fullerenes, and/or zeolites.
  • the substrate can be titania, silica and/or alumina.
  • the substrate can be a titanium oxide.
  • the titanium oxide support substrate can include anatase and/or the commercially available P25.
  • the substrate can be monolithic.
  • the substrate can have a planar surface such as a plate or disc.
  • the substrate can be particulate.
  • the substrate can comprise nanoparticles. In one embodiment, the substrate comprises titanium dioxide nanoparticles.
  • the catalyst can be a photocatalyst that is activated by light.
  • the source of ultraviolet light may be from a dedicated lamp or may be from a natural light source, such as the sun.
  • Photocatalysts are described above, and all description made there applies here unless the context makes clear otherwise.
  • An advantage of using photocatalysts (when compared to other types of catalysts) is that they often do not require the use of heat to catalyse reactions. Not requiring heat can decrease operational costs, make the production of hydrogen more environmentally friendly, and make the production of hydrogen safer.
  • Temperatures that can be used for photocatalysis are around room temperature e.g. about 20-30 °C, but may be as high at about 100-300 "C, for example 250 °C. Nevertheless, the photocatalyst could be used with the addition of heat, which may allow for a reduction in light energy input.
  • the active metal of the catalyst can be selected from one or more of gold, copper, silver, platinum, palladium, nickel, rhenium, ruthenium and/or titanium, and/or other transition metals and their corresponding oxides.
  • the active metal comprises only ruthenium.
  • the active metals comprise gold and ruthenium.
  • the active metal can comprise gold and ruthenium bound together.
  • the gold and ruthenium can have a bond distance in the range of from about 2.5 to 3 A. such as 2.7 1 2.8 A, or at least about 2.5, 2.7, 2.8 or 3 Angstrom (A).
  • the gold x to ruthenium y ratio can be a bout 1 : 1.5, 1 : 2, 1 : 3.
  • the active metal can be AuRu 3 .,Au 2 Ru 3 and or AuaRu4.
  • the AuRu 3 can be Ru 3 AuPPh 3 CI ⁇ CO)i 0 .
  • the active metal can be present in the form of complexes, nanoparticles and/or clusters
  • the active metals are present as a nanocluster.
  • Clusters or nanoclusters (referred to herein interchangeably unless the context makes clear otherwise), in yet a further form, refer to a collection or group of two or more active metal atoms, but usually contain less than approximately 200 atoms. It terms of size, nanoclusters are usually considered as being between complexes a nd nanoparticles.
  • the na nocluster can comprise more than 20 metal atoms with a distribution of ⁇ 10 or more percent e.g. M 3 o ⁇ 3, M 5 s ⁇ 5, MmoilO.
  • the metals that comprise the nanoclusters can comprise ligands.
  • any ligands associated with the nanocluster can be used to stabilise the nanocluster and in some circumstances may help to improve the performance of the na nocluster when as a catalyst.
  • the nanocluster with ligands is of the form ula I n some cases, it is preferred to remove any ligands before the compound is used as a catalyst.
  • the ligands assist in the cata lytic activity.
  • the activity of the photocata lyst may decrease.
  • the nanoclusters have a n average size of less than about 2.5, 2, 1.5 or 1 nm.
  • An active site for reaction can com prise more than one or more na noclusters.
  • the catalyst can be applied to a support.
  • the support can be particulate itself or can be a solid substrate.
  • the solid substrate can be a wafer such as a silicon wafer or a porous silica disk.
  • the first cata lyst in the form of a paste can be applied to the support.
  • the thickness of the applied cata lyst can be varied.
  • the nanoclusters can be supported by e.g. titanium dioxide nanoparticles.
  • the number of nanoclusters per substrate nanoparticle may depend on the type of active metal used . In one embodiment, the number of nanoclusters per nanoparticle is at least about 1, 2, 5, 10, 15, 20, 15 or 30.
  • the percentage approximate coverage of the nanoparticles with nanoclusters can be at least in the ra nge of from about 0.1 to 10 % or more, or about 0.1, 0.5, 1, 1.7, 2, 3, 4, 5, 6 or 10 % or more as a percentage of the tota l availa ble surface area.
  • the method can comprise contacting a photocataiyst with water and C02 in order to photocatalyse the reaction of water with C02, wherein the photocataiyst comprises gold nanoclusters and ruthenium nanoclusters or mixed gold-ruthenium nanoclusters supported by a titanium dioxide substrate.
  • the catalyst can be pre-treated prior to use.
  • Treatment methods can include calcining and/or acid treatment. Acid treatment can be performed with or without calcining. Where calcining is used, acid treatment can be performed before or after calcining. It is thought that acid treatment has an effect on the interaction between the catalyst substrate and the active metal during preparation of the catalyst.
  • Heterogeneous catalysts and photocatalysts are generally pre-treated in situ before testing, in order to remove advantageous hydrocarbons and other surface-adsorbed species, or to open up catalyst active sites by removal of ligands.
  • Many different techniques for this can be undertaken for example including ozone treatment, calcination in C»2 or H2, and heating under a flow of inert gas.
  • any treatment does not have any damaging effect upon active metal clusters which might cause them or the substrates to which they are attached to aggregate into larger nanoparticles.
  • Calcining can be performed under oxygen and/or hydrogen atmospheres and/or under vacuum.
  • Calcining can be performed at a temperature of not more than about 50, 100, 200, 300 or 400 °C. !n an embodiment, the calcining is undertaken at about 200 °C under vacuum.
  • H 2 gas production There is thought to be improvement in H 2 gas production as the catalyst is treated under successively harsher conditions. This may be due to the removal of any ligands from the catalyst surface (leaving only the active metal clusters behind). It is hypothesised that in some embodiments, the removal of ligands and an increase in particle size improves the catalytic performance of anatase-supported clusters.
  • the catalyst can be advantageous to expose the catalyst to a vacuum for an extended prior of time. Prior to use the catalyst can be held under vacuum for at least about 1, 2, 5, 10, 12 or 15 hours. It is preferred that the catalyst is not exposed to the atmosphere once it has been held under vacuum.
  • the step of contacting the catalyst with water can involve exposing all or some of the surface(s) of catalyst with water in order to effect a reaction.
  • the water can be from any source and the various ways in which the surface of the catalyst can contact water are described above, and also apply here unless the context makes clear otherwise.
  • the catalyst is also exposed to carbon dioxide.
  • Preliminary testing indicates a P C O2:PH2O ratio of about 2, 3 or 4 is optimal for solar fuel production.
  • the Pcoi'-Pmo ratio is 3.
  • optimal production of CO and H 2 was observed at a reagent ratio of 1:1, and C0 2 :H 2 0 ratios in the range of at feast about 0.5 to 4, preferably about 1 to about 3, give peak hydroca rbon production.
  • oxygen is also produced according to the following equation (1):
  • the hyd rogen can be used for the production of unsubstituted hydrocarbons. Additional hydrogen can be injected into the system if desired.
  • Hydrocarbons can include Ci to Cio containing compounds such as methane, ethane, propa ne, butane, pentane, hexane, heptane, octane, nonane, decane, their various isomeric forms such as n-, iso-, sec- and tert-alka nes, and their respective oxides such as methanol and etha nol. More complex hydrocarbons such as aromatics may also be prod uced.
  • the hydrocarbons produced can be greater than Cio.
  • the hydrogen ca n also be used for the formation of a substituted hydroca rbon such as methanol, ethanol, propanol, and so on.
  • Hydrogen can be converted into methane using the Sabatier reaction shown in equation (2): Hydrogen can be converted into methanol using the following eq uation (3):
  • the catalyst is able to stabilise intermediaries in reaction (1) such as hyd rogen rad icals, hydronium and or hydroxylradicals that go on to react with C0 2 .
  • the amount of hydrogen that can be produced by the Au-Ru catalyst can be at least about 70, 80, 90 or 100 ⁇ hr 1 g ⁇ cm "2 .
  • the amount of methane, ethane, ethene, propane a nd/or propene that can be produced in step (b) can be at least about 350, 450, 550, 1000, 2000 or 5000 nmol hr 1 g "1 cm "2 .
  • the reaction of steps (a) and (b) may be performed in an apparatus (a reactor).
  • the apparatus can have an inlet for the introduction of water.
  • the catalyst may be housed in a part of the apparatus and a rranged so that the water can come into contact with the surface of the catalyst.
  • the a ppa ratus is sealable once the water has been introduced.
  • the water can be introduced as a liquid or vapour. If the water is a vapour it can be introduced under pressure.
  • a light source can be arranged inside or outside of the vessel to allow activation of the cata lyst.
  • the temperature and/or pressure within the reactor may be slowly increased to effect the optimal reaction.
  • the apparatus can have an inlet for the introduction of ca rbon dioxide.
  • the catalyst may be housed in a part of the appa ratus and arranged so that the carbon dioxide can come into contact with the surface of the catalyst.
  • the appa ratus is sealabie once the carbon dioxide has been introduced.
  • the carbon dioxide is continuously introduced into the appa ratus.
  • the reaction temperature can be elevated to at least about 120, 150, 180 or 200 °C .
  • the gases evolved in the reactor may be collected from the apparatus from an outlet. The gases may be collected and separated.
  • an apparatus for the production of hydrocarbon(s) such as methane or substituted hydrocarbons such as methanol, the apparatus ada pted to undertake the method described herein.
  • hyd rocarbons or substituted hydrocarbons when prod uced by a method as described herein, or when prod uced in an appa ratus herein described .
  • a catalyst when used in the method or apparatus of the invention.
  • Figure 1 graph showing H 2 gas yield for benchma rk Pt-TiC>2 photocata lysts and control experiments; the latter of which showed no i production.
  • Figure 2 Bar chart showing a compa rison of mean H2 peak production rates for samples that were exposed to vacuum in the reaction cell for 10 minutes, com pared with those that were evacuated for 12 hours. Acid-washed supports are denoted with the a/w abbreviation.
  • Figure 3 Graph showing the number of moles of O2 and C0 2 in the reaction cell throughout the course of an extended experiment, showing the consumption of 0 2 and peak C0 2 prod uction.
  • Figure 4 Ba r chart showing average H 2 peak production rate for Au s clusters supported on pure anatase nanopartides with various treatments.
  • Figure 5 Ba r chart showing average H 2 peak production rate for Aug clusters supported on pure anatase and acid-washed P25 nanopartides with various treatments.
  • Figure 6 Ba r chart showing average H 2 peak production rate for Auioi clusters supported on acid- washed P25, treatments, acid-washed anatase, and pure anatase nanopartides with various treatments
  • Figure 7 Bar chart showing a comparison of H2 peak production rate for Aus, Aug, and Auioi clusters supported on anatase nanoparticies with various treatments.
  • Figure 8 Bar chart showing a comparison of H 2 peak production rate for Aua, Aug, and Auioi clusters supported acid-washed P25 nanoparticies with various treatments.
  • Figure 9 Bar chart showing a comparison of h1 ⁇ 2 peak prod uction rate for 0.17% w/w Auioi, Au g , and Aus clusters supported on Ti0 2 against 1.0% w/w Pt-P25 and 1.0% w/w Pt-anatase.
  • Figure 10 Graph showing hydrocarbon production following photocatalyst treatment at varying calcination temperature. The reaction temperature was set at 220 °C for each of the runs.
  • Figure 11 early experimental data on ruthenium nanoclusters (RU3) in step (b).
  • Figure 12 early experimental data on ruthenium nanoclusters ⁇ RU3) in step (b).
  • Figure 13 early experimental data on ruthenium nanoclusters (RU3) in step (b).
  • Figure 14 early experimental data on ruthenium nanoclusters in step (b).
  • FIG. 15A-H early experimental data on gold nanoparticies in step (a).
  • Figure 16B Peak production rates of longer-chain hydrocarbon prod ucts by various photocatalysts tested . Standa rd reaction conditions were used for all tests.
  • Figure 17 B Peak production rates of longer-chain hydrocarbon products by various photocatalysts tested, normalised to total precious metal content of co-catalysts.
  • Figure 18A Peak production rates of (left) H2 a nd (right) CH4 by all cluster-deposited titania materials tested here. Standard reaction conditions were used for a ll tests.
  • Figure 18B Peak prod uction rates of longer-chain hydrocarbon prod ucts by all cluster- deposited titania materials tested here.
  • Figure 19 Peak production rates of Ha by all cluster-deposited titania materia ls, in atmospheres of H 2 0/Ar and HzO/CC /Ar. Standard reaction conditions were used for ail tests, with CO2 neglected in the case of H 2 0/Ar atmospheres.
  • Figure 20B Peak production rates of longer-chain hydrocarbon products by AuRuj-TiC as a function of combined material pre-treatment and reaction temperature.
  • PCO2:PH2O 3 for all tests here.
  • Figure 21A Peak production rates of hydrogen, methane and CO by AURU3-T1O2 as a function of reaction tem perature. Pcoi'-Pmo - 3, pre-treatment temperature of 200 °C for a ll tests here.
  • Figure 21B Peak production rates of longer-chain hydrocarbon products by Au RurTi0 2 as a function of reaction temperature.
  • PCO2'.PHIO 3, pre-treatment temperature of 200 °C for all tests here.
  • Figure 22 shows bond distances in Ru3(p-AuPPh 3 )(p-CI)(CO)i 0 . Examples of embodiments of the invention
  • An aqueous stock solution of 50 m gold chloride anions (AuCU " ) in a glass vial was made by dissolving HAuCU 3 H2O with the same molar amount of HCI, ensuring stability for more than several months.
  • An aqueous stock solution of 50m borohydride anions (BH " ) in a glass beaker was made by dissolving Na BF gra nules with the same molar amount of NaOH, guaranteeing stability for several hours at room temperature.
  • the amount of the BH/f/OH " solution was increased from 300 to 650 uL followed by heating for 2-3 min at the boiling temperature of water on a hot plate.
  • the average diameter of gold nanoparticles was precisely controlled from 3.2 to 5.2 nm.
  • the amount of the BH4 ' /O H " solution was changed from 200 to 1300 ⁇ . during the search for the "sweet zone" before heating.
  • Nanoparticles can be prepared by this method as described in the paper entitled: Cha rged Gold Nanoparticles in Non-Polar Solvents: 10 Minute Synthesis and 2D Self-Assembly, LANG M U IR, 26(10) pp7410-7417 (2010), the entire contents of which are hereby incorporated by reference in their entirety. If there are any inconsistencies between this document and the incorporated document, this document shall take precedence unless the context ma kes clear otherwise.
  • va rious control experiments were also performed to ensure that the water vapour was the source of H 2 production. Experiments were performed at 28 °C with 20 Torr of H 2 0 vapour and 280 Torr of Ar in the reaction cell at the start of the experiment, with 20.7 mW cm "2 of UV light irradiating the sample disc, eq uivalent to ⁇ 4.5 suns worth of UV intensity (assuming UV ⁇ 400 nm) .
  • Pt-P25 and Pt-anatase have average i production rates of 77.1 ⁇ 9.9 and 45.6 ⁇ 12.7 ⁇ hr 1 g "1 cm “2 , respectively.
  • the unplatinised samples do not produce any notable amounts of H 2 as the rate of electron-hole recombination is too high to afford a ny detectable levels of H 2 , as Ti0 2 cannot split water photocatalytica lly without co-catalysts.
  • the increased performance observed for Pt-P25 compared with Pt-anatase could be due to the mixed polymorphs of anatase, rutile, and amorphous T1O2 present in these nanoparticles, which has been demonstrated to provide a greater degree of charge separation during photo-excitation, as well as possible synergistic effects between anatase and rutile.
  • pre-treatment before hydrogen production includes no pre-treatment ( Figure 15a, f), calcining at 200 °C followed by vacuum ( Figure 15b-d), calcining at 200 °C ( Figure 15e), and calcining 200 °C in the presence of oxygen ( Figure 15g, h).
  • the rate of hydrogen production was usually less than approximately 160 ⁇ hr 1 g -1 cnrr 2 .
  • the Auioi nanoclusters used in the following experiments have a size of approximately 1.4 nm and have a much increased hydrogen production yield.
  • Table 1 A table summarising the different pre- and post-treatments applied to the supported Au clusters used in photocatalytic experiments.
  • Table 2 A table sowing a summary of the key trends in ligand loss and agglomeration observed for Au8, Au9, Aull and AulOl on acid-washed P25 and pure anatase supports under the various post-treatment conditions.
  • Table 2 summarises the key changes to the physical properties of these catalysts due to the various treatments.
  • ligand loss and agglomeration with successively harsher post-treatment conditions. This effect is far more pronounced for clusters supported on pure anatase nanoparticles than on the acid-washed P25 nanoparticles, showing the strong effect of acidic pre-treatment on the interaction between the Ti0 2 surface and Au clusters.
  • For samples on either support there is general evidence for two cluster states after post-treatment, with one portion remaining unchanged, while the other undergoes some level of agglomeration.
  • the peak H 2 production rates for Aus/anatase with various treatments are shown in Figure 4.
  • the Aus/anatase samples have peak H 2 production rates of 17.92 ⁇ 3.22, 51.74 ⁇ 5.17, and 71.12 ⁇ 7.11 ⁇ hr 1 g ⁇ crrf 2 for the untreated, calcined at 200 °C under 0 2 , and calcined at 200 °C under 0 2 +H 2 treatments, respectively.
  • the average H 2 production rates for Aug supported on anatase and acid-washed P25 nanoparticles with various treatments are shown in Figure 5.
  • the Au 9 /anatase samples have H 2 production rates of 33.5 ⁇ 3.35 and 112.9 ⁇ 12.3 ⁇ hr "1 g "1 cm “2 for untreated and calcined under 0 2 samples, respectively.
  • the acid-washed P25 supported samples yield H 2 production rates of 82.7 ⁇ 8.27, 511.4 ⁇ 51.1, and 75.3 ⁇ 7.53 ⁇ hr 1 g ⁇ cm "2 for the untreated, heat treated under vacuum, and calcined under 0 2 samples respectively.
  • the untreated Aug/acid-washed P25 has a greater performance than untreated Aug/anatase, as the former results in virtually no change in the size or ligand coverage of the Aug clusters after they are supported.
  • Heat treatment at 200 °C results in agglomeration of a portion of the Aug clusters while still ligand-protected, while the other portion lose some ligands, forming Au-0 bonds, and begin to agglomerate. There is also evidence that of the portion that loses ligands, some may not agglomerate.
  • the production rates are 534.8 ⁇ 53.5, 112.2 ⁇ 11.2, and 122.7 ⁇ 11.2 ⁇ hr "1 g _1 cm “2 for the untreated, calcined under 0 2 , and calcined under 0 2 and H 2 samples respectively.
  • the production rates are 238.3 ⁇ 16.5, 437.5 ⁇ 43.7, and 188.8 ⁇ 34.0 ⁇ hr 1 g "1 cm "2 for the untreated, heat treated, and calcined under 0 2 samples respectively.
  • Figure 7 shows a comparison between Au 8 , Au 9 , and Auioi clusters supported on anatase nanoparticles. Similar trends are observed for all three clusters as successively harsher post- treatments are applied. When samples are calcined under an 0 2 atmosphere, their H 2 production rate increased compared to their untreated counterparts. When samples are calcined under 0 2 and H 2 , a harsher and prolonged calcination, their H 2 production rate is increased beyond that of samples calcined under O2 alone.
  • Aug calcined under 0 2 and H2 There is no data available for Aug calcined under 0 2 and H2, although it can be assumed that it would follow the same trend as the other clusters, given that Aug calcined under 0 2 has a production rate within experimental error of the production rate for Auioi calcined under 0 2 .
  • Figure 8 shows the similar trends in H2 production rates for both clusters after treatment, whereby 200 °C heat treatment of the clusters results In a large increase in performance compared to the untreated samples, followed by a decrease in performance for the calcined under 0 2 samples.
  • the production rate of the heat treated samples are within the experimental error of each other, and the size measurement by the H TE are also within sampling error of each other (2.4 ⁇ 1.7 vs 3.2 + 1.7 nm for Aug and Auioi, respectively). Therefore, the similar production rate measured for these two clusters on acid-washed P25 with the same treatment could be because the two samples are of similar size after agglomeration, while still being protected by a comparable number of ligands.
  • the production of H2 from photocatalytic water-splitting experiments was accompanied by the production of C0 2 and consumption of 0 2 .
  • the C0 2 by-product arises from the well-known capacity for TiC>2 to photo-oxidise organic contaminants, and consumes the stoichiometrically evolved O2 from the water-splitting reaction throughout the experiment.
  • the source of carbon in the reaction cell is most likely from unavoidable adventitious carbon that is present in all vacuum systems and samples exposed to atmosphere, in addition to the possible contribution from oil back-streaming from the rotary pump.
  • Various carbon based sealant material used in the reaction cell and adsorbed CO may also contribute to the source of carbon.
  • O2 present in the reaction cell at the beginning of the experiment due to low vacuum is likely rapidly consumed by quenching defect states within the Ti0 2 nanoparticles and by photo-adsorption of 0 2 to the T1O2 surface over the initial hour of experiments.
  • This initial O2 presence could also include O2 molecules adsorbed to the T1O2 surface at ambient temperature, or those adsorbed to the walis of the reaction cell.
  • the formation of surface Oz ⁇ and Of species during this period by molecular 0 2 likely behaves as electron traps or hole scavengers after photo-excitation, increasing electron-hole separation, which could explain the decrease in both H 2 and CO2 production after the excess 0 2 in the reaction cell is consumed.
  • Example 12 RU3 nanoctusters on titania
  • Ru clusters have interesting properties when it comes to catalysis and these are mostly unexplored.
  • the materials explored in this example are ligand stabilised clusters on a titania support. All the experiments were conducted at 2 bar with a 4:1 ratio of H2 to CO2. All Ru clusters were loaded at 0.17% on titania.
  • the gases produced are 379 ⁇ -1 g "1 of methane, 4649 ⁇ 1 of CO and 149 ⁇ ⁇ ⁇ 1 of ethane.
  • Ruthenium nanoparticles at a 3% loading produced in the range of 2000-3000 ⁇ "1 of methane, but had 20 times more Ru than the cluster samples. Production rate normalised to Ru mass shows that Ru clusters out-perform the ruthenium nanoparticles by almost 4 times as much. .
  • Example 14 The effect of the thickness of the photocatalyst in step (b)
  • Example 15 Photocatalytic Studies ofAuRuz Deposited upon Anatase TIOi
  • the cluster was deposited upon anatase T1O2, (hereinafter referred to as "AURU3-T1O2") and was evaluated for photocatalytic solar fuel production in the gas-phase, using a heterogeneous batch reactor apparatus.
  • H2 and methane were detected as the major products of these reactions, with longer-chain hydrocarbons up to C4 species observed as minor products under certain conditions.
  • Photocatalytic production rates of methane and hydrogen by anatase Ti0 2 , AuRU3/Ti02 and Pt/Ti0 are shown in Figure 16A.
  • Production rates of minor, longer-chain hydrocarbon products are then shown in Figure 16B.
  • Deposition of the AuRu 3 cluster improves the turnover of both major and minor hydrocarbon products relative to bare anatase, with methane production increasing by ⁇ 3 ⁇ and ethane by a factor of two.
  • the minor hydrocarbon products the large uncertainties make interpretation of this data difficult. These errors are predominantly due to the extremely low levels of these products generated ("10-100 ppb), giving poor signal-to-noise ratios in the GC-FID.
  • Figures 17A and 17B show the same production rates discussed above, but instead normalized to the total precious metal content (Pt or Au/Ru) deposited upon the Ti0 2 nanoparticles.
  • Pt or Au/Ru precious metal content
  • the cluster-based AuRu 3 /Ti0 2 out-performs Pt/Ti0 2 in the generation of all products detected here.
  • platinum nanoparticles can be highly-active co-catalysts for C0 2 photo-reduction this is extremely promising for potentially further improving the efficiency of these reactions by use of sub-nanometer clusters instead of nanoparticles.
  • Example 16 A comparison between the catalysts: AuRus/TI02, RU3/T1O2 and RU4/HO2
  • Ru3/Ti0 2 again gives the lowest catalytic efficiency, with Ru 4 /Ti0 2 and AuRu 3 /Ti0 2 yielding higher production rates.
  • both AURU3/T1O2 and RU4/T1O2 give comparable methane production rates. Similar trends are observed for most of the minor hydrocarbon products, with large experimental uncertainties in production rates of ethane, propane and propene again preventing further conclusions from being drawn. The exception to this is ethene, for which Ru 4 /Ti0 2 generates appreciably greater amounts than either of the other two photocatalysts.
  • Heterogeneous catalysts and photocatalysts are generally pre-treated in situ before testing, in order to remove advantageous hydrocarbons and other surface-adsorbed species, or to open up catalyst active sites by removal of !igands.
  • Many different techniques for this can be undertaken for example including ozone treatment, calcination in O2 or H2, and heating under a flow of inert gas.
  • the inventors work demonstrates that many of these treatments have damaging effects upon clusters deposited upon T1O2, often causing aggregation to larger nanoparticles. This is undesirable in developing cluster-based catalytic materials, as it removes the size-specific nature of the cluster co-catalysts and complicates the correlation of catalytic activity to particle size.
  • selection of an appropriate pre-treatment which removes adsorbed contaminants while still retaining intact clusters upon the surface for these materials is paramount.
  • Heating under vacuum was selected for catalyst pre-treatment, as it was shown to have the least aggregative properties of material treatments studied. All photocata lytic materials discussed above were heated to 200 °C while pumping under vacuum for 20 minutes. However, a range of temperatures from 50 - 250 °C (the limit of the apparatus) were also tested for AURU3/T1O2.
  • Figures 20A and 20B show the dependence of photocata lytic activity upon this pre-treatment temperature for major and minor products, respectively. It should be noted that throughout these experiments, the reaction temperature was kept the same as the pre-treatment temperature. This was done to ensure that no samples were tested at higher temperatures than they were pre-treated, such that any observed change in chemical state could be ascribed to the treatment and not the reaction.
  • the reaction may be limited by adsorption-desorption effects upon the Ti0 2 surface, where the rate-limiting step is desorption of products at lower temperatures, and adsorption of reagent molecules at higher temperatures. Reacting at 150 °C may achieve an optimal equilibrium between reagent adsorption and product desorption. At lower temperatures, poor desorption of products or intermediates from water reduction could simultaneously limit the H 2 production rate and proton transfer to C0 2 . As the reaction temperature then increases these reduced states of water would then be mobilized and more readily desorbed, allowing for formation of C-H bonds and giving greater H2 production rates. However, on rising above 150 °C the limiting factor could then become reagent adsorption, with the excess thermal energy in the system causing molecules to desorb from the T1O2 surface before completing photocatalytic transformations and hence decreasing overall production rates.

Abstract

L'invention concerne un procédé de production d'hydrocarbure(s), tel que du méthane, ou d'hydrocarbures substitués, tels que du méthanol, le procédé comprenant les étapes consistant à mettre en contact un premier catalyseur avec de l'eau afin de photocatalyser la séparation d'au moins une partie de l'eau en hydrogène et en oxygène; et l'entrée en contact d'un second catalyseur avec un courant gazeux comprenant du dioxyde de carbone et au moins une partie de l'hydrogène produit dans l'étape (a) afin de photocatalyser la réaction entre l'hydrogène et le dioxyde de carbone pour produire un ou plusieurs hydrocarbures, comme du méthane, et/ou des hydrocarbures substitués, comme du méthanol. Dans un mode de réalisation, le catalyseur comprend des nanoagrégats d'or et/ou de ruthénium supportés sur un substrat.
EP16869409.9A 2015-11-30 2016-11-30 Conversion photocatalytique de dioxyde de carbone et d'eau en hydrocarbure(s) substitué(s) ou non substitué(s) Withdrawn EP3383529A4 (fr)

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WO2018232060A2 (fr) * 2017-06-15 2018-12-20 Sabic Global Technologies B.V. Production de méthanol à partir d'un procédé de dissociation de l'eau
GB2581791A (en) * 2019-02-25 2020-09-02 Univ Belfast Method and apparatus for alkane oxidation
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AT526005A2 (de) 2022-03-24 2023-10-15 Fachhochschule Salzburg Gmbh Photochemisches Verfahren zur Erzeugung von Alkoholen
WO2024013181A1 (fr) * 2022-07-12 2024-01-18 Nanogap Sub-Nm-Powder, S.A. Catalyseurs à agrégats quantiques atomiques (aqc) supportés par un oxyde métallique en tant que porteurs d'oxygène pour des procédés en boucle chimique
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